The present invention relates to the use of certain N-aminoalkyl alkylpiperazines, especially 1-(3-aminopropyl)-2,5-dimethylpiperazine (APDP), as promoters for alkaline salts in "hot pot" type acid gas scrubbing processes.
Recently, it was shown in U.S. Pat. No. 4,112,050 that sterically hindered amines are superior to diethanolamine (DEA) as promoters for alkaline salts in the "hot pot" acid gas scrubbing process. U.S. Pat. No. 4,094,957 describes an improvement to this process whereby amino acids, especially sterically hindered amino acids, serve to prevent phase separation of the aqueous solution containing sterically hindered amines at high temperatures and low fractional conversions during the acid gas scrubbing process.
One of the preferred sterically hindered amines described in these patents is N-cyclohexyl-1,3-propanediamine. The bulky cyclohexane ring on this diamino compound provides steric hindrance to the carbamate formed at this site thereby favoring the expulsion of CO.sub.2 during regeneration, thereby leaving the hindered amine group free to protonate. The primary amino group of this diamino compound assists in maintaining solubility under lean conditions. Under lean conditions when there is insufficient carbonic acid present to protonate the hindered amino group, the molecule would be insoluble were it not for the primary amino group which forms a stable polar carbamate ion. However, even the carbamated primary amino group is insufficient to prevent insolubility of the compound under very lean conditions and an additional additive, as proposed in U.S. Pat. No. 4,094,957, an amino acid, is required to maintain solubility of the diamino compound. This amino acid also contributes to additional capacity and faster absorption rates for carbon dioxide, so it therefore acts as a copromoter in addition to solubilizing the sterically hindered diamino compound. Screening studies of available amino acids as possible copromoters for N-cyclohexyl 1,3-propanediamine based on cyclic capacity and rates of absorption ascertained that pipecolinic acid was one of the best amino acid copromoters.
Subsequent studies, however, have demonstrated that the N-cyclohexyl-1,3-propanediamine/pipecolinic acid promoter system has several shortcomings. First, N-cyclohexyl-1,3-propanediamine is both chemically unstable and volatile. For example, it degrades into a cyclic urea, especially in the presence of hydrogen sulfide. In fact, the rate of cyclic urea formation has been found to be highly dependent on hydrogen sulfide concentration, a common contaminant of industrial acid gas streams. The cyclic urea formation from this diamine is favored by the stability of the six-membered ring structure of the cyclic urea. In addition to promoter losses due to cyclic urea formation, which may be a serious problem with hydrogen sulfide rich streams, the cyclic urea product has limited solubility, and its separation from solution poses additional problems. Various techniques for coping with this water insoluble cyclic urea have been proposed. See, for example, U.S. Pat. Nos. 4,180,548 and 4,183,903. However, these techniques have specific benefits and problems, e.g., specialized equipment is necessary.
Pipecolinic acid also has shortcomings, e.g., it is rather expensive and its picoline precursor is in limited supply.
In view of the commercial potential of using the sterically hindered amino compounds as described and claimed in U.S. Pat. Nos. 4,094,957 and 4,112,050, there is a need for finding sterically hindered amino compounds which perform as well as N-cyclohexyl-1,3-propanediamine but do not have the volatility and degradation problems of this compound.
Also, U.S. Pat. Nos. 4,094,957 and 4,112,050 disclose various other sterically hindered amines, including specific piperazine compounds. These specifically identified piperazines have been found to be too volatile for economic utilization on large scale acid gas treating facilities. Also, there is a need for finding a less costly replacement for pipecolinic acid which possesses its effectiveness. Preferably, there is a need for finding a single amino compound which performs as well or nearly as well as the N-cyclohexyl-1,3-propane-diamine/pipecolinic acid mixture, but does not suffer the preparative cost, volatility and degradation problems of this mixture. Such a discovery would be of significant technical and economic merit.
Various amino acids have been proposed as promoters for alkaline salts in the "hot pot" gas scrubbing process. For example, British Pat. No. 1,305,718 describes the use of beta and gamma amino acids as promoters for alkaline salts in the "hot pot" acid gas treating process. These amino acids, however, are not suitable because the beta-amino acids undergo deamination when heated in aqueous potassium carbonate solutions. The gamma amino acids form insoluble lactams under the same conditions. Also, the alphaamino acid, N-cyclohexyl glycine, as described in Belgian Pat. No. 767,105, forms an insoluble diketopiperazine when heated in aqueous solutions containing potassium carbonate.